CN1196798A - Circular-dichroism optical element, device thereof and liquid crystal polymer - Google Patents

Circular-dichroism optical element, device thereof and liquid crystal polymer Download PDF

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CN1196798A
CN1196798A CN97190737A CN97190737A CN1196798A CN 1196798 A CN1196798 A CN 1196798A CN 97190737 A CN97190737 A CN 97190737A CN 97190737 A CN97190737 A CN 97190737A CN 1196798 A CN1196798 A CN 1196798A
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dichroism
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CN1109902C (en
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本村弘则
泉今日子
中野秀作
望月周
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Nitto Denko Corp
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    • C09K19/00—Liquid crystal materials
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    • C09K19/3857—Poly(meth)acrylate derivatives containing at least one asymmetric carbon atom
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    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

A circular dichroism optical element having the solidified layer of a liquid crystal polymer comprising a Grandjean oriented cholesteric liquid crystal phase, a liquid crystal display apparatus using the optical element, and a liquid crystal polymer composed of, as the component, a copolymer comprising at least two kinds of specific acrylic monomer units.

Description

Circular-dichroism optical element and device thereof and liquid crystal polymer
Technical field
The present invention relates to a kind of circular-dichroism optical element that constitutes by the liquid crystal polymer cured layer and utilize the liquid crystal indicator or the backlight unit of the good brightness of this element, and be applicable to the liquid crystal polymer that forms said optical element.
Background technology
Known circular-dichroism optical element of past is the liquid cholesteric crystal of a kind of low-molecular-weight is encapsulated into state of orientation between the substrate of glass etc. and makes.In this optical element, the screw axis of liquid crystal molecule is vertical Ge Shi orientation (Grandjeanoriented) with respect to optical element, when a kind of natural light (incident angle is 0 degree) when being parallel to said screw axis incident, in this natural light, the light of certain wavelength has half circularly polarized light that revolves as right (or left side) to be reflected approximately, remaining makes an appointment with half to see through as the circularly polarized light that a left side (or right) revolves, this light wavelength λ determines (in the formula by formula: λ=np, n is the mean refractive index of liquid crystal, and p is cholesteric helical pitch).The left side of the circularly polarized light that is reflected in addition, or dextrorotation are by the spiral status of cholesterol phase decision and consistent with the sense of rotation of spiral.
In the optical element of above-mentioned circular-dichroism, because incident light is separated into reflected light and sees through light, therefore its reflected light also might be utilized, and can expect the substitute of the conduct Polarizer that the absorption dichroic dye is made on oriented films such as polyvinyl alcohol (PVA).In a word, said Polarizer majority is used for liquid crystal indicator etc., but, the light that sees through as rectilinearly polarized light only is below 50% of incident light, remaining light is absorbed in the Polarizer, can not be used, so this is to be difficult to make liquid crystal indicator to reach one of reason of high brightnessization and low power consumptionization.
Yet, for circular-dichroism optical element before and since must with above-mentioned substrate and usefulness, therefore become not only thick but also heavy, thereby become the obstacle of the light weight of liquid crystal indicator and slim property etc., this is its shortcoming.In addition, the state of orientation of cholesteric crystal, for example pitch changes with conditions such as temperature easily, and this is its another shortcoming.
Though also the someone proposed cholesterol liquid crystal polymkeric substance (seeing that the spy opens clear 55-21479 communique and U.S. Pat 5332522 instructionss), but be difficult to obtain to resemble the solidfied materials such as film of good state of orientation the low molecular weight material, and need the long-time of a few hours in order to carry out orientation process, low and the poor durability of its glass transition temperature, therefore lack practicality, in a word, all be difficult to obtain the circular-dichroism optical element of solid states such as film in either case.
The objective of the invention is to obtain that a kind of solidfied material by liquid crystal polymer constitutes, thin and light, and state of orientation not labile circular-dichroism optical element under applied temps such as its pitch.Another object of the present invention is to obtain a kind of like this liquid crystal polymer, the film forming of this liquid crystal polymer is good, and can form the Ge Shi orientation with good single crystal domains state, its orientation process only needs can finish in the short time of waiting in several minutes, can immobilization stably under vitreousness, thereby can form all good circular-dichroism optical element of a kind of durability and storage stability, and the pitch of its cholesterol phase is controlled easily.
Disclosure of an invention
The invention provides a kind of circular-dichroism optical element, it is characterized in that, it has the liquid crystal polymer cured layer that the cholesteric crystal by Ge Shi orientation constitutes mutually; The present invention also provides a kind of liquid crystal polymer, it is characterized in that, it be the multipolymer that forms of monomeric unit 40～5 weight % with monomeric unit 60～95 weight % of following general formula (a) expression and general formula (b) expression as its constituent,
Said general formula (a) is:
Figure A9719073700051
(in the formula, R 1Expression hydrogen or methyl, m represents 1～6 integer, X 1Expression CO 2Base or OCO base, p and q represent 1 or 2 and satisfy p+q=3.)
Said general formula (b) is
Figure A9719073700052
(in the formula, R 2Expression hydrogen or methyl, n represents 1～6 integer, X 2Expression CO 2Base or OCO base, X 3Expression-CO-R 3Or-R 4, wherein, R 3Expression
Figure A9719073700061
Or R 4Expression
Figure A9719073700063
And R 5Expression
Figure A9719073700064
Or
Figure A9719073700065
).
According to above-mentioned formation, can obtain a kind ofly to form state of orientation not labile circular-dichroism optical elements under applied temps such as its pitch by thin and light liquid crystal polymer solidfied material.In addition, use liquid crystal polymer of the present invention, can under the good condition of film forming, easily form a kind of film with Ge Shi orientation of good single crystal domains state, the short time that its orientation process only needed wait in several minutes can finish, and immobilization under the condition of vitreousness can be stable at, can form a kind of durability and all good circular-dichroism optical element of storage stability efficiently, and the pitch of its cholesterol phase is control easily also, therefore also can easily obtain a kind of optical element that shows circular-dichroism in the visible region.
Simple declaration to accompanying drawing
Fig. 1 represents the sectional view of liquid crystal indicator one example.
Fig. 2 represents the sectional view of another routine liquid crystal indicator.
Fig. 3 is a curve map, the relation between the centre wavelength of the containing ratio of the monomeric unit of its expression general formula (b) and demonstration circular-dichroism.
Fig. 4 is a curve map, it represent another kind of general formula (b) monomeric unit containing ratio and show relation between the centre wavelength of circular-dichroism.
Fig. 5 is the curve map of expression light transmission features.
Fig. 6 is the curve map of the another kind of light transmission features of expression.
Fig. 7 also is the curve map of the another kind of light transmission features of expression.
Fig. 8 also is the curve map of the another kind of light transmission features of expression.
Fig. 9 also is the curve map of the another kind of light transmission features of expression.
Figure 10 also is the curve map of the another kind of light transmission features of expression.
Figure 11 also is the curve map of the another kind of light transmission features of expression.
Figure 12 also is the curve map of the another kind of light transmission features of expression.
Figure 13 also is the curve map of the another kind of light transmission features of expression.
Fig. 14 also is the curve map of the another kind of light transmission features of expression.
Figure 15 also is the curve map of the another kind of light transmission features of expression.
The preferred plan that is used to carry out an invention
Optical element of the present invention is the liquid crystal polymer cured layer that constitutes mutually of a kind of cholesteric crystal that has by Ge Shi orientation and the optical element that can show circular-dichroism.When forming said optical element, can use suitable liquid crystal polymer, but preferably use a kind of with following general formula (a) expression monomeric unit and the monomeric unit of general formula (b) expression as the multipolymer of composition.
Said general formula (a) is: (in the formula, R 1Expression hydrogen or methyl, m represents 1～6 integer, X 1Expression CO 2Base or OCO base, p and q represent 1 or 2 and satisfy p+q=3.)
Said general formula (b) is
Figure A9719073700072
(in the formula, R 2Expression hydrogen or methyl, n represents 1～6 integer, X 2Expression CO 2Base or OCO base, X 3Expression-CO-R 3Or-R 4, wherein, R 3Expression Or
Figure A9719073700074
R 4Expression And R 5Expression Or
The acrylic monomer that can form the monomeric unit of above-mentioned general formula (a), general formula (b) expression can be synthetic by suitable method.Illustrate in passing, the synthesis example of the acrylic monomer of formula (a1) expression is shown below.
That is to say, in above-mentioned flow process, at first with potassium iodide as catalyzer with ethylene chlorhydrin and 4-hydroxybenzoic acid reflux in alkaline aqueous solution, obtain hydroxycarboxylic acid, then itself and acrylic or methacrylic acid are carried out dehydration, obtain (methyl) acrylate, then in the presence of DCC (dicyclohexyl carbodiimide) and DMAP (dimethylamino naphthyridine) with (methyl) acrylate of being obtained with 4-cyano group-4 '-xenol carries out esterification treatment, thereby obtains (a1) as the purpose product.
The synthesis example of the acrylic monomer of formula (b1) expression is shown in addition, below.
Figure A9719073700091
In above-mentioned flow process, at first with potassium iodide as catalyzer with hydroxyalkyl halogen and 4-hydroxybenzoic acid reflux in alkaline aqueous solution, obtain hydroxycarboxylic acid, then itself and acrylic or methacrylic acid are carried out dehydration, obtain (methyl) acrylate, in the presence of DCC and DMAP, (methyl) acrylate that is obtained is had the R of containing with a kind of on 4 then 3The phenol of the CO base of base carries out esterification treatment, thereby obtains (b1) as the purpose product.
Above-mentioned have the R of containing on 4 3The phenol of the CO base of base, for example method obtains as described below, just at first methylchloroformate and 4-hydroxybenzoic acid is reacted in alkaline aqueous solution, obtains carboxylic acid, then this carboxylic acid is transformed into acyl chlorides with oxalyl chloride, then with its in pyridine/tetrahydrofuran with H-R 3Reaction, thus import R 3Base, at last with its with WITH AMMONIA TREATMENT removing its protecting group, thereby obtain a kind ofly on 4, have the R of containing 3The phenol of the CO base of base. In above-mentioned formula (b1) synthetic, if the compound that adds in the finishing operation
Figure A9719073700102
Replace with following compound, can obtain acrylic monomer by formula (b2) expression.
Figure A9719073700111
That is to say, with hydroxycarboxylic acid and (methyl) thus acrylic acid carries out after dehydration obtains (methyl) acrylate, in the presence of DCC and DMAP, (methyl) acrylate that is obtained is carried out esterification treatment with a kind of phenol that has the unsymmetrical carbon group on 4, can obtain purpose product (b2).
The above-mentioned phenol that on 4, has the unsymmetrical carbon group, method as described below for example, that is, and by with the 4-hydroxy benzaldehyde with (S)-(-)-the 1-phenylethylamine carries out azeotropic dehydration and makes in toluene.
Figure A9719073700112
Therefore, other acrylic monomers that can form the monomeric unit of being represented by general formula (a), general formula (b) also can use the suitable raw material with required importing group that it is synthetic according to above-mentioned synthesis example.
The liquid crystal polymer that is used to form optical element is by one or more of the monomeric unit of above-mentioned general formula (a) expression, and carries out copolymerization by one or more of the monomeric unit of general formula (b) expression and forms.Its copolymerization ratio preferably accounts for 60～95 weight % by the monomeric unit of general formula (a) expression, monomeric unit by general formula (b) expression accounts for 40～5 weight %, if the containing ratio by the monomeric unit of general formula (b) expression is too much, its liquid crystal liquid crystal property variation then, if containing ratio is very few, its cholesteric crystal variation then.
If the molecular weight of multipolymer is too small, its film forming variation then, if excessive, then could variation as the orientation of liquid crystal and single crystal domains voltinism thereof, be difficult to form uniform state of orientation, so its weight-average molecular weight is suitably 2,000～100,000, preferably 2,500～50,000.
The preparation of multipolymer for example can be carried out according to the polymerization methods of the acrylic monomer of routines such as free radical polymerization mode, cationic polymerization mode, anionic polymerisation mode.Under the situation of using the free radical polymerization mode, can use various polymerization initiators, still wherein preferred the use resembles azoisobutyronitrile and crosses nitrogenize benzoyl etc., and its decomposition temperature is not high not low yet, is comparing the initiating agent that decomposes under the moderate moisture.
The pitch of cholesteric crystal changes along with the variation of the containing ratio of the monomeric unit of being represented by general formula (b) in the multipolymer.Fig. 3 and Fig. 4 example of passing the imperial examinations at the provincial level shows said containing ratio and shows relation between the centre wavelength of circular-dichroism.In addition, in the curve of Fig. 3, use in the following embodiments with (a2) of chemical formulation with (b3) as the monomer component of multipolymer, and in the next use of the situation of Fig. 4 (a2) with (b6) as the monomer component of multipolymer.The wavelength that shows circular-dichroism is determined by said pitch, therefore, by the containing ratio of control by the monomeric unit of general formula (b) expression, promptly can regulate the wavelength that shows circular-dichroism.Therefore, as described in the following examples, can easily obtain the light of visible region is shown the optical element of circular-dichroism.
One or more multipolymer can be mixed and form optical element.Also can regulate the wavelength region may that shows circular-dichroism by the different two or more multipolymers of wavelength region may that show circular-dichroism are mixed.In the present invention, consider from viewpoints such as the stability of orientation characteristics such as the durability of obtaining optical element and pitch temperature variation during or no changes, preferably use glass transition temperature to form optical element in the liquid crystal polymer more than 80 ℃ to practical application.
In addition, in the present invention, can use by one or more formations of the monomeric unit of above-mentioned general formula (a) or general formula (b) expression, the homopolymer that meets this general formula forms optical element as the hybrid type liquid crystal polymkeric substance by the polymkeric substance of the polymkeric substance of general formula (a) class and general formula (b) class.Its blending ratio or molecular weight etc. can decide according to above-mentioned multipolymer.
The optical element that shows circular-dichroism can form according to method for orientation treatment before.As its object lesson, can enumerate following method, for example, at first on substrate, form the alignment films that constitutes by polyimide or polyvinyl alcohol (PVA) etc., use these alignment films of friction treatment such as rayon cloth then, be higher than glass transition temperature again at developping solution crystalline polymer on this alignment films and with it and be lower than under the temperature in the isotropic transition temperature range and heating, then it is cooled to below the glass transition temperature, so that the molecule of liquid crystal polymer becomes glassy state according to the Ge Shi state of orientation, thereby form a kind of by the immobilized cured layer of required orientation.
As above-mentioned substrate, for example can use suitable substrates such as the film that forms by tri acetyl cellulose or polyvinyl alcohol (PVA), polyimide or poly-aromatic compounds, polyester or polycarbonate, polysulfones or polyethersulfone, as plastics such as epoxy resin or glass plate.The liquid crystal polymer cured layer that on substrate, forms, can with its with substrate as a whole thing be directly used in optical element, also it can be stripped down from substrate, use as the optical element that constitutes by film etc.
Liquid crystal polymer can be launched by the mode of heating and melting, launches after also can being made into solution with solvent.As solvent, for example can use The suitable solvent such as methylene chloride or cyclohexane, triclene or tetrachloroethane, N-Methyl pyrrolidone or tetrahydrofuran.Launching the coating machine that it is suitable that operation can be used rod coater, rotary coating machine or roll coater etc. carries out.
If the thickness of formed liquid crystal polymer cured layer is thin excessively, then be difficult to show circular-dichroism, if it is blocked up, its even orientation variation then, can not show circular-dichroism, and required time of orientation process is longer, so the thickness of cured layer is suitably 0.5～20 μ m, wherein is preferably 1～10 μ m.In addition, when forming optical element, can be as required, be used the polymkeric substance beyond the said multipolymer and stabilizing agent, plastifier etc. are inorganic, organic or metal species etc. constitutes various adjuvants.
Though optical element of the present invention can show circular-dichroism, concerning the liquid crystal cured layer of individual layer, can show that the wavelength coverage of circular-dichroism is limited.This restricted portion usually near the 1.00nm wavelength region may, but in optical element being applied to equipment such as liquid crystal indicator the time, generally always wish that it can show circular-dichroism in the Zone Full of visible light.
In the present invention, gather into folds by the liquid crystal polymer that can show circular-dichroism to the light of different wave length is solidified lamination, thereby the wavelength region may that shows circular-dichroism can be enlarged.The advantage of this laminationization is, except can enlarging said wavelength coverage, can also adapt to the wavelength that oblique incidence light causes and move.The lamination processing can be carried out different combinations by the centre wavelength to the reflection circle polarized light, makes two-layer above lamination product.When lamination, preferably use bonding agent etc., to reduce as far as possible in each surface reflection loss at the interface.
Explanation in passing, can make up the liquid crystal polymer cured layer of the centre wavelength of reflection circle polarized light according to the circularly polarized light that reflects equidirectional at 300～900nm, and the centre wavelength of selecting reflection different, the circularly polarized light of difference more than 50nm makes up mutually, like this by long-pending folded 2～6 kinds of cured layers just can form a kind of in very wide wavelength coverage the optical element of demonstration circular-dichroism.In addition, the purpose that the cured layer of the circularly polarized light of reflection equidirectional is combined is consistent in order to make by the phasic state of the circularly polarized light of each layer reflection, thereby prevent to become in the different polarized condition of each wavelength region may, so just can utilize again, thereby reach the purpose of raising the efficiency by the circularly polarized light with reflection such as reflection horizon.
Optical element of the present invention is based on its circular-dichroism, incident light can be resolved into the circularly polarized light of left and right two kinds of rotation modes, and with it respectively as seeing through the output of light and reflected light, and its visual angle width is good, very little by the caused changes in optical properties of visual angle change, therefore can be applicable to well from vergence direction also can Direct observation the various devices of liquid crystal indicators such as direct viewing type etc.Particularly can utilize the circularly polarized light that is reflected again by reflection horizon etc., thereby can reach the purpose of utilizing effect that improves light, and also can easily reach large tracts of landization etc., therefore can use as the back lighting system in the liquid crystal indicator well.
The liquid crystal indicator that optical element of the present invention is used for the back lighting system has been shown in Fig. 1 and Fig. 2.Wherein, the 4th, back lighting system, the 1st, the optical element of this system, the 2nd, be used to make circularly polarized light to be transformed into the phase separation layer of rectilinearly polarized light, the 3rd, light source, the 5th, Polarizer, the 6th, liquid crystal cell, 11, the 12, the 13rd, be used to form the liquid crystal polymer cured layer of stack-up type optical element, the 31st, light source anchor clamps, the 41, the 44th, light diffusing sheet, the 42nd, luminescent layer, 43, the 46th, reflection horizon, the 45th, spatial accommodation, the 7th, the light path polarizer of compensation usefulness.
Liquid crystal indicator is normally suitably assembled the compensation of Polarizer, liquid crystal cell, back lighting system and use as required with members such as light path polarizers, driving circuit pack into then and make, and in the present invention, shown in legend, except light is incided liquid crystal cell 6 this point by optical element 1 and the phase separation layer 2 that is used to make circularly polarized light be transformed into rectilinearly polarized light, all the other all do not have particular determination, can form according to method before.
Therefore, so long as the liquid crystal indicator that a kind of sure light that makes polarized light state incides in the liquid crystal cell get final product.Preferred use stable twisted nematic liquid crystal or STN Super TN type liquid crystal, but be non-stable twisted nematic liquid crystal and be scattered in the liquid crystal and the host and guest's nematic crystal that forms by dichroic dye, perhaps dielectricity liquid crystal etc. also can use by force.Type of drive to liquid crystal does not have particular determination yet.
Though shown in the example of accompanying drawing, have Polarizer 5 in the both sides of liquid crystal cell 6,, when can export the good light of linear polarization by optical element etc. the time, can save the Polarizer of back lighting side.This linear polarizationization just makes the linear polarizationization through the circularly polarized light of optical element, can be undertaken by the phase separation layer 2 that is configured on the optical element 1.Therefore, liquid crystal cell can be configured in and be on the intrasystem phase separation layer 2 of back lighting.
The purpose that is used to make circularly polarized light through optical element to be transformed into the phase separation layer of rectilinearly polarized light is the phase place that changes by the circularly polarized light of optical element outgoing, be converted into the state that a kind of rectilinearly polarized light composition occupies the majority, thereby make light easily see through Polarizer etc.Therefore, should be able to make the circularly polarized light by the outgoing of light element be transformed into a kind of rectilinearly polarized light that is equivalent to 1/4 wavelength phase differential as preferred phase separation layer most ofly, and can make the light of other wavelength be transformed into and a kind ofly have the major diameter direction as much as possible with on the direction that above-mentioned rectilinearly polarized light parallels, and approach the flat elliptically polarized light of rectilinearly polarized light as much as possible.
By disposing aforesaid phase separation layer, just the major diameter direction according to rectilinearly polarized light direction that makes emergent light or elliptically polarized light disposes with a mode that parallels that sees through of Polarizer as much as possible, thereby obtains a kind of light of the state that can occupy the majority through the rectilinearly polarized light composition of Polarizer.
Phase separation layer can form with suitable material.Wherein preferably transparent and can give the material of homogeneous phase potential difference.In general, single orientation thing of the polarizer that is formed by the plastic tensile film of polycarbonate and so on, nematic crystal polymkeric substance or twist alignment thing etc. all are fit to use.The phase differential of phase separation layer can be according to the decisions aptly such as wavelength coverage by the circularly polarized light of optical element outgoing.For example, in the visible region, consider from viewpoints such as wavelength characteristic and practicality, nearly all polarizer all mixes the material that some can show the wavelength dispersion of positive birefringence according to its material characteristic, can use the less material of phase differential as a rule, wherein preferably using phase differential is 100～200 material.
Phase separation layer can be used as 1 layer or 2 layers with on form.Constituting by 1 layer under the situation of phase separation layer, the material that birefringent wavelength dispersion is more little, the polarized condition of each wavelength is even more, and is therefore comparatively preferred.On the other hand, overlappingization of phase separation layer can be improved the wavelength characteristic in the wavelength region may effectively, and its array mode can be according to decisions aptly such as wavelength region may.
In addition, be that object forms under the situation of phase separation layer more than 2 layers with the visible region, as mentioned above, from considering, preferably contain the phase separation layer that odd-level more than 1 layer can be given 100～200nm phase differential for the viewpoint that obtains the light that a kind of rectilinearly polarized light composition occupies the majority.Phase separation layer except the phase separation layer that can give 100～200nm phase differential is considered from the viewpoint of improving wavelength characteristic, preferably forms by a kind of phase separation layer that can give 200～400nm phase differential, but unqualified to this.
Above illustrative liquid crystal indicator, because the bottom surface of illuminator is provided with reflection horizon 43,46 overleaf, therefore can be the circularly polarized light that is reflected by optical element 1 by said reflective layer reflects, it is incided in the optical element once more as reflected light, thereby reached the purpose that improves the utilization ratio of light.That is to say, circularly polarized light by the optical element reflection is constrained between optical element and the reflection horizon, and reflected repeatedly, become and can see through the circularly polarized light state of optical element, thus can reduce since the light that reflection loss etc. cause do not utilize part.
As mentioned above, owing to utilize phase separation layer that circularly polarized light is transformed into rectilinearly polarized light, therefore can reduce the containing ratio of the light component that can be absorbed by Polarizer, and the light that becomes reflection loss and absorption loss in the past also can preferably utilize, therefore the utilization ratio of light can be improved, thereby a kind of liquid crystal indicator bright, that observation property is good can be formed.
As above-mentioned reflection horizon, preferably resemble the reflection horizon that can produce the reflection counter-rotating the metal covering that forms by aluminium and silver etc.Therefore, it can make the left rotation and right rotation direction of the circularly polarized light of reflection reverse, and makes it become the state identical with the circularly polarized light that sees through, and can improve through efficient as much as possible, thereby can improve the utilization ratio of light effectively.In addition,, also can solve because the situation that the polarized condition that causes of its diffusion randomly mixes, thereby can improve the utilization ratio of light even for being the diffusive reflective layer of representative with the male and fomale(M﹠F).
As luminescent layer, suitable those luminescent layers on an one side that uses with beam projecting.Preferably those not absorbing light and can be effectively with the material of light outgoing.The light source 3 of linear light sources such as (hot and cold) cathode tube or light emitting diode etc. is configured in the side of light guide plate (42), make the light that in this light guide plate, transmits, by effect such as diffusion, reflection, diffraction, interference from a side outgoing of this light guide plate, in liquid crystal indicator, known example has side light type back lighting (Fig. 1) and EL bulb type or directly descends bulb type (Fig. 2).In addition, optical element can be configured in the light exit side of said luminescent layer.
The aforesaid light guide plate that is used for light that inside is transmitted from an one side outgoing, for example can be by on a kind of light-emitting face of transparent or semitransparent resin plate or in its inside, a kind of point-like or banded diffuser being set, perhaps be provided with and can form the object of concaveconvex structure in the resin plate the inside and make.
When forming luminescent layer, can be as required the light diffusing sheet 41,44 that is used to obtain uniformly light-emitting, be used to control the prismatic lens of beam projecting direction, be used for a reflection unit that the light that leaks returns, be used for the servicing unit from light source anchor clamps 31 grades of the light of linear light source outgoing guiding light guide plate side is configured in preposition, thereby obtain the device of suitable combination.
In addition, show by the good contrast of the incident acquisition of rectilinearly polarized light highly in order to make, as Polarizer, particularly as the Polarizer of back lighting side, just as near the Polarizer of the side optical element of visible light light incident side that is configured in liquid crystal cell, preferably use the high Polarizers of degree of polarization such as absorption-type straight line polarizer of iodine series for example or series dye.
The formation member of liquid crystal indicator and back lighting system etc. can be integrated as lamination with it, also can make it keep released state.In addition; when forming liquid crystal indicator, can suitably dispose the compensation that for example is arranged on diffuser plate and light shield layer, antireflection film, protective seam or fender on the Polarizer of observing side, be arranged between liquid crystal cell and the Polarizer with the optical element that polarizer etc. is fit to.In addition, under the situation that optical element and phase separation layer are used in combination, can their laminations is integrated, also can make it keep released state.Their allocation position should become optical element between the light exit side of luminescent layer and the state between the phase separation layer.
Above-mentioned compensation is to be used for the compensated birefringence performance to the dependence of wavelength with the purpose of polarizer, thereby improves its observing effect etc., this polarizer in Fig. 1 and Fig. 2 with symbol 7 expressions.In the present invention, this polarizer such as can be configured between the liquid crystal cell of observing side and/or background illumination side and the Polarizer as required at the position.In addition, the polarizer of usefulness by way of compensation can use suitable polarizer according to wavelength region may etc., and can be with it as the overlapping layer moulding more than 1 layer or 2 layers.
As mentioned above, the circularly polarized light that liquid crystal indicator of the present invention is reflected by optical element by means of handles such as reflection horizon carries out the polarized light conversion and utilizes as emergent light again, thereby prevent reflection loss, and this emergent light is carried out phase control by means of phase separation layer, make it be transformed into the light state of the rectilinearly polarized light composition that is rich in the Polarizer permeability, therefore prevented to be absorbed the loss that causes, thereby improved the utilization ratio of light by Polarizer.
By the light of phase separation layer outgoing, become to grade as the major diameter direction of rectilinearly polarized light or elliptically polarized light, the rectilinearly polarized light composition that preferably wherein can see through Polarizer accounts for more than 65%, more preferably accounts for more than 70%.In addition, consider that with optical element during with the phase separation layer combination, the preferably feasible incident light that is made of natural light is as the polarized light outgoing of a kind of look changes delta ab based on the NBS mode at the state below 10 from the viewpoint of the change color that prevents to show.The laminationization of liquid crystal polymer cured layer considers it also is favourable from the viewpoint that reduces said change color.
The fast axis of the polarizing axis of the Polarizer of back lighting side in the case, and phasic difference plate or the arrangement angles between the slow axes can determine aptly according to the phase difference characteristics of phase separation layer and the characteristic of incident circularly polarized light etc.For example, under the situation of the polarizer of the above-mentioned phase differential that can give 100～200nm, when left circularly polarized light incident, with the polarizing axis of Polarizer as benchmark (0 degree), then the arrangement angles of the fast axis of polarizer is 0～90 when spending, be preferably 35～55 when spending, be preferably 45 especially when spending, can improve the transmittance of Polarizer.
On the other hand, when right-handed polarized light incident, can set above-mentioned angle according to the slow axes of polarizer, thereby can improve the transmittance of Polarizer.Under the situation with polarizer more than 2 layers, when the phase separation layer that particularly wherein can give 100～200nm phase differential occupied outermost superficial layer, dextrorotation was to be that benchmark is set said arrangement angles with this layer.Embodiment 1
Figure A9719073700181
Will be in tetrahydrofuran 430ml by above-mentioned chemical formula (a2) monomer 33.9 weight portions of representing (82mmol) and monomer 9.16 weight portions (18mmol) heating for dissolving of representing by chemical formula (b3), make its temperature stabilization between 55～60 ℃, use the nitrogen replacement reactor inner space then, under the condition that does not have oxygen to exist, splash into the tetrahydrofuran solution 5ml that is dissolved with azoisobutyronitrile 0.5 weight portion, carry out 6 hours polyreaction, obtaining reactant liquor is under agitation slowly injected ether 3000ml, obtain the polymer precipitation of white, with dry after this sediment centrifuging, then it is precipitated 2 times so that its purifying again, obtain a kind of weight-average molecular weight and be 7000 multipolymer.The glass transition temperature of this multipolymer is 88 ℃, and the isotropic transition temperature is 225 ℃, presents cholesterol structural under the temperature between the two.
Be on the tri acetyl cellulose film of 50 μ m the polyvinyl alcohol layer that a layer thickness is about 0.1 μ m to be set at a layer thickness; with rayon cloth this layer is carried out friction treatment; use rod coater on above-mentioned treated side, to apply a kind of dichloromethane solution that contains the above-mentioned multipolymer of 10 weight %; treat the heating orientation process that carried out 15 minutes its dry back under 140 ℃ temperature; at room temperature put then cold, thereby make the immobilization under the glassy state that is oriented in of liquid crystal polymer.The thickness of this liquid crystalline polymer layer is 2 μ m; the film like optical element that is made of the integrated thing of this layer and tri acetyl cellulose film demonstrates the circular-dichroism as the mirror-like reflect blue light, and this reflected light is that a kind of wavelength is the left circularly polarized light of 410～485nm.The light transmission features of this optical element is shown among Fig. 5.Embodiment 2
Except using according to the ratio of monomer 6.11 weight portions (12mmol) of monomer 36.3 weight portions (88mmol) of chemical formula (a2) and chemical formula (b3), all the other carry out according to the step of embodiment 1, obtain a kind of weight-average molecular weight and be 7500 multipolymer, and make optical element with it.The glass transition temperature of this multipolymer is 92 ℃, and the isotropic transition temperature is 240 ℃, presents cholesterol structural under the temperature between the two.In addition, this optical element demonstrates the circular-dichroism as the mirror-like reflection red light, and this reflected light is that a kind of wavelength is the left circularly polarized light of 580～695nm.The light transmission features of this optical element is shown among Fig. 6.Embodiment 3
The multipolymer that step according to embodiment 1 and embodiment 2 is obtained mixes according to the ratio of 0.47/0.53 (embodiment 1/ embodiment 2), and the method according to embodiment 1 makes optical element then.This optical element demonstrates the circular-dichroism of mirror-like reflects green, and this reflected light is that a kind of wavelength is the left circularly polarized light of 480～585nm.The light transmission features of this optical element is shown among Fig. 7.Embodiment 4
Figure A9719073700191
Except using according to the ratio of monomer 9.18 weight portions (20mmol) of monomer 17.1 weight portions (40mmol) of monomer 16.5 weight portions (40mmol) of chemical formula (a2), above-mentioned chemical formula (a3) and chemical formula (b4), all the other carry out according to the step of embodiment 1, obtain a kind of weight-average molecular weight and be 11500 multipolymer.The glass transition temperature of this multipolymer is 105 ℃, and the isotropic transition temperature is 238 ℃, presents cholesterol structural under the temperature between the two.
On the other hand, use above-mentioned multipolymer, carry out 15 minutes orientation process according to the method for embodiment 1 under 150 ℃ temperature, to form a kind of thickness be the liquid crystal polymer cured layer of 3 μ m and obtained optical element by this condition.This optical element demonstrates a kind of circular-dichroism of mirror-like reflect red sodium yellow, and this reflected light is that a kind of wavelength is the right-circularly polarized light of 565～675nm.The light transmission features of this optical element is shown among Fig. 8.Embodiment 5
Except using according to the ratio of monomer 9.09 weight portions (15mmol) of monomer 36.3 weight portions (85mmol) of following chemical formula (a4) and chemical formula (b5), all the other carry out according to the step of embodiment 1, obtain a kind of weight-average molecular weight and be 21000 multipolymer.The glass transition temperature of this multipolymer is 95 ℃, and the isotropic transition temperature is 215 ℃, presents cholesterol structural under the temperature between the two.
Figure A9719073700202
On the other hand, use above-mentioned multipolymer, to form a kind of thickness be the liquid crystal polymer cured layer of 5 μ m and obtained optical element according to the method for embodiment 1.This optical element demonstrates a kind of circular-dichroism of mirror-like reflection red light, and this reflected light is that a kind of wavelength is the right-circularly polarized light of 590～695nm.In addition, the light transmission features of this optical element is shown among Fig. 9.Embodiment 6
The optical element that method according to embodiment 1,2,3 is obtained is superimposed together by the acrylic compounds bonding coat, obtains a kind of optical element that shows circular-dichroism in the scope of wavelength 410～690nm.The light transmission features of this optical element is shown among Figure 10.
One 1/4 wavelength plate that the laminate of 2 oriented films that are made of polycarbonate is made, superimposed on above-mentioned optical element by the acrylic compounds bonding coat, when natural light incides on this optical element, be 3 based on the look changes delta ab of NBS mode, this numerical value is very little.In addition, the heat test that this set is had the optical element of 1/4 wavelength plate under 80 ℃ temperature, carried out 1000 hours, perhaps under the condition of 60 ℃ and 90%RH, carry out 1000 hours warm test, the result shows, all almost do not observe the variation of optical property or outward appearance etc. in any test, this shows that it has good durability.
In addition, use the above-mentioned optical element that is provided with 1/4 wavelength plate, form a kind of liquid crystal indicator of structure as shown in Figure 1, this device demonstrates 90cd/m 2Brightness, this shows its (60cd/m when not using said optical element 2) improve 50% brightness.Embodiment 7
Figure A9719073700211
Except with monomer 10.2 weight portions (23mmol) heating for dissolving of monomer 31.8 weight portions (77mmol) of above-mentioned chemical formula (a2) expression and above-mentioned chemical formula (b6) expression is in tetrahydrofuran 415ml, all the other are all according to the step of embodiment 1, having obtained a kind of weight-average molecular weight is 7300, glass transition temperature is 85 ℃, the isotropic transition temperature is 215 ℃, the multipolymer that presents cholesterol structural under the temperature between the two, use the method for this multipolymer according to embodiment 1, under 150 ℃, carry out the processing mode of 5 minutes heating orientations, obtained a kind of circular-dichroism that can show as the mirror-like reflect blue light, its reflected light is that a kind of wavelength is the optical element of the left circularly polarized light of 410～485nm, and the light transmission features of this optical element is shown among Figure 11.Embodiment 8
Except monomer 35.5 weight portions (86mmol) according to chemical formula (a2), outside the ratio of monomer 6.20 weight portions (14mmol) of chemical formula (b6) is used, all the other are all according to the method for embodiment 7, have obtained a kind of weight-average molecular weight and be 7100 multipolymer, and have made optical element with it.The glass transition temperature of this multipolymer is 89 ℃, and the isotropic transition temperature is 230 ℃, presents cholesteric structure under the temperature between the two.In addition, this optical element demonstrates the circular-dichroism as the mirror-like reflection red light, and this reflected light is that a kind of wavelength is the left-hand polarization light of 580～695nm.The light transmission features of this optical element is shown among Figure 12.Embodiment 9
Mixing according to the ratio of 0.47/0.53 (embodiment 7/ embodiment 8), make optical element according to the method for embodiment 7 according to the multipolymer of embodiment 7 and embodiment 8.This optical element demonstrates the circular-dichroism as the mirror-like reflects green, and this reflected light is that a kind of wavelength is the left circularly polarized light of 480～585nm.The light transmission features of this optical element is shown among Figure 13.Embodiment 10
The optical element that obtains according to embodiment 7,8,9 is superimposed together by the acrylic compounds bonding coat, has obtained a kind of optical element that in the scope of wavelength 410～690nm, shows circular-dichroism.The light transmission features of this optical element is shown among Figure 14.
One 1/4 wavelength plate that the laminate of 2 oriented films that are made of polycarbonate is made, superimposed on above-mentioned optical element by the acrylic compounds bonding coat, when natural light incides on this optical element, be 3 based on the look changes delta ab of NBS mode, this numerical value is very little.In addition, the heat test that this set is had the optical element of 1/4 wavelength plate under 80 ℃ temperature, carried out 1000 hours, perhaps under the condition of 60 ℃ and 90%RH, carry out 1000 hours warm test, the result shows, all almost do not observe the variation of optical property or outward appearance etc. in any test, this shows that it has good durability.
In addition, use the above-mentioned optical element that is provided with 1/4 wavelength plate, form a kind of liquid crystal indicator of structure as shown in Figure 1, this device demonstrates 90cd/m 2Brightness, this shows its (60cd/m when not using said optical element 2) improve 50% brightness.Comparative example
Except monomer 39.0 weight portions (80mmol) according to following chemical formula (C), outside the ratio of monomer 9.14 weight portions (20mmol) of chemical formula (D) was used, all the other were all according to the method for embodiment 1, had obtained a kind of weight-average molecular weight and be 18000 multipolymer.The glass transition temperature of this multipolymer is 71 ℃, and the isotropic transition temperature is 205 ℃, presents cholesterol structural under the temperature between the two.
On the other hand, use above-mentioned multipolymer, form the cured layer of liquid crystal polymer according to the method test of embodiment 1, the result can not obtain the orientation thing of homogeneous, prepared thickness is the reflection that the liquid crystalline polymer layer of 3 μ m can not display mirror, and demonstrating scattered reflection, is the inadequate product of a kind of circular-dichroism.The light transmission features of this optical element is shown among Figure 15.In addition, can think that this scattered reflection causes owing to not forming the Ge Shi orientation.
The possibility of industrial utilization
According to the present invention, can obtain a kind of that constitute by the liquid crystal polymer solidfied material, thin and light, state of orientation not labile circular-dichroism optical elements under applied temps such as its pitch, the film forming of this liquid crystal polymer is good, can form the Ge Shi orientation with good single crystal domains state.Can in the short time of waiting in several minutes, finish orientation process, immobilization under the condition of vitreousness can be stable at, thereby can form all good circular-dichroism optical element of a kind of durability and storage stability, and can obtain a kind of liquid crystal polymer of the easy control of pitch of cholesterol phase.

Claims (9)

1. a circular-dichroism optical element is characterized in that, it has a kind of cured layer of the liquid crystal polymer that is made of mutually the cholesteric crystal of Ge Shi (Grandjean) orientation.
2. optical element as claimed in claim 1, liquid crystal polymer wherein has the glass transition temperature more than 80 ℃, and with a kind of contain by the monomeric unit of following general formula (a) expression and by the multipolymer of the monomeric unit of general formula (b) expression as its constituent
Said general formula (a) is:
Figure A9719073700021
(in the formula, R 1Expression hydrogen or methyl, m represents 1～6 integer, X 1Expression CO 2Base or OCO base, p and q represent 1 or 2 and satisfy p+q=3.)
Said general formula (b) is
Figure A9719073700022
(in the formula, R 2Expression hydrogen or methyl, n represents 1～6 integer, X 2Expression CO 2Base or OCO base, X 3Expression-CO-R 3Or-R 4, wherein, R 3Expression Or And R 4Expression R 5Expression
Figure A9719073700031
Or
Figure A9719073700032
3. optical element as claimed in claim 1 or 2, this optical element shows circular-dichroism to the light of visible region.
4. as the described optical element of claim 1～3, it is shown that by a kind of light to different wave length the laminate of cured layer of the liquid crystal polymer of circular-dichroism constitutes.
5. as the described optical element of claim 1～4, it has can make circularly polarized light be transformed into the phase separation layer of rectilinearly polarized light.
6. optical element as claimed in claim 5, it can be the incident light that is made of natural light as based on the look changes delta ab of the NBS mode polarized light outgoing at 10 following states.
7. a liquid crystal indicator is characterized in that, the light incident side that it observes light at liquid crystal cell has the optical element described in the claim 1～6.
8. a backlight unit is characterized in that, it has the optical element described in the claim 1～6 at light exit side.
9. a liquid crystal polymer is characterized in that, the multipolymer that it constitutes with monomeric unit 40～5 weight % by monomeric unit 60～95 weight % of the described general formula of claim 2 (a) expression and general formula (b) expression is as constituent.
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